CN103857623A - Silicon oxide for negative electrode material of nonaqueous electroltye secondary cell, method for producing same, lithium ion secondary cell, and electrochemical capacitor - Google Patents

Silicon oxide for negative electrode material of nonaqueous electroltye secondary cell, method for producing same, lithium ion secondary cell, and electrochemical capacitor Download PDF

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CN103857623A
CN103857623A CN201280049685.8A CN201280049685A CN103857623A CN 103857623 A CN103857623 A CN 103857623A CN 201280049685 A CN201280049685 A CN 201280049685A CN 103857623 A CN103857623 A CN 103857623A
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oxide
secondary cell
negative electrode
electrode material
electrolyte secondary
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CN103857623B (en
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福冈宏文
上野进
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Shin Etsu Chemical Co Ltd
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Abstract

The present invention is a silicon oxide for the negative electrode material of a nonaqueous electrolyte secondary cell, wherein the silicon oxide for the negative electrode material of a nonaqueous electrolyte secondary cell is a carbon-containing silicon oxide obtained by coprecipitation from SiO gas and a carbon-containing gas and the carbon content of the carbon-containing silicon oxide is between 0.5 and 30%. The present invention thereby provides a silicon oxide with which, when used as the negative electrode material, a nonaqueous electrolyte secondary cell having excellent cycle properties and high cell capacity can be produced, a method for producing the silicon oxide, and a lithium ion secondary cell and electrochemical capacitor that use the silicon oxide.

Description

Si oxide, its manufacture method, lithium-ion secondary cell and electrochemical capacitor for non-aqueous electrolyte secondary cell negative electrode material
Technical field
The present invention relates to a kind of Si oxide, its manufacture method for non-aqueous electrolyte secondary cell negative electrode material, use lithium-ion secondary cell and the electrochemical capacitor of described non-aqueous electrolyte secondary cell negative electrode material Si oxide, described non-aqueous electrolyte secondary cell negative electrode material in the time using as lithium ion secondary battery cathode active substance, has heavy body and good cycle characteristics with Si oxide.
Background technology
In recent years, be accompanied by the remarkable development of portable electric appts, communication equipment etc., consider the rechargeable nonaqueous electrolytic battery of a kind of high-energy-density of active demand from the miniaturization of economy and equipment, light-weighted viewpoint.At present, as the scheme that makes this rechargeable nonaqueous electrolytic battery high capacity, such as known have a following method: negative material uses the oxide compound of boron (B), titanium (Ti), vanadium (V), manganese (Mn), cobalt (Co), iron (Fe), nickel (Ni), chromium (Cr), niobium (Nb) and molybdenum (Mo) etc. and the method (patent documentation 1,2) of composite oxides thereof; The M that molten metal is quenched 100-xsi xthe method (patent documentation 3) that (x > 50at%, M=Ni, Fe, Co, Mn) uses as negative material; Negative material uses the method (patent documentation 4) of the oxide compound of silicon; And negative material uses Si 2n 2o, Ge 2n 2o and Sn 2n 2the method (patent documentation 5) of O etc.
[prior art document]
(patent documentation)
Patent documentation 1: No. 3008228 communique of Japanese Patent
Patent documentation 2: No. 3242751 communique of Japanese Patent
Patent documentation 3: No. 3846661 communique of Japanese Patent
Patent documentation 4: No. 2997741 communique of Japanese Patent
Patent documentation 5: No. 3918311 communique of Japanese Patent
Summary of the invention
[inventing problem to be solved]
In above-mentioned materials, though Si oxide can be labeled as SiO x(wherein, because x is oxidation overlay film, therefore 1 slightly large than theoretical value), but using in the analysis of X-ray diffraction, what take is to be about the non-crystalline silicon fine structure that be scattered in silicon-dioxide of several nanometers to tens nanometers.Therefore, although compared to silicon, its cell container is less, if compared with carbon, per unit weight is high 5～6 times, and volumetric expansion is also less, and cycle characteristics is also comparatively good, can be considered as more practical negative material.
But as vehicle-mounted use, cycle characteristics is still insufficient, need to improve cycle characteristics, make cycle characteristics reach that namely carbon material is identical with existing negative material.
[solving the method for problem]
The present invention completes in view of the above problems, object is to provide a kind of Si oxide, its manufacture method, the lithium-ion secondary cell that uses described Si oxide and electrochemical capacitor, by described Si oxide is used as negative material, can make a kind of have excellent cycle characteristics and the rechargeable nonaqueous electrolytic battery of high cell container.
To achieve these goals, the invention provides a kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide, it is characterized in that, it is by making SiO gas and carbonaceous gas jointly deposit the carbon containing Si oxide that (codeposit) obtains, and the carbon content of described carbon containing Si oxide is 0.5～30%.
If this carbon containing Si oxide, in the situation that using as negative material, owing to can making the rechargeable nonaqueous electrolytic battery that cell container is high and cycle characteristics is excellent, therefore, can become the non-aqueous electrolyte secondary cell negative electrode material Si oxide of high-quality.
Now, preferably: not SiC (silicon carbide) change of carbon that aforementioned carbon containing Si oxide is contained.
Like this, if the not carbon containing Si oxide of SiCization of the carbon containing, negative material can be made the rechargeable nonaqueous electrolytic battery of the abundant height of a kind of cell container and cycle characteristics excellence of Si oxide.
Now, preferably: the median size of aforementioned carbon containing Si oxide is 0.1～30 μ m, BET specific surface area (BET specific surface area) is 0.5～30m 2/ g.
If this carbon containing Si oxide, in the situation that making non-aqueous electrolyte secondary cell negative electrode material, the cementability in the time coating electrode is good with Si oxide for non-aqueous electrolyte secondary cell negative electrode material, can fully improve cell container.
In addition, the invention provides the manufacture method of a kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide, it is the method for manufacturing non-aqueous electrolyte secondary cell negative electrode material Si oxide, it is characterized in that, the raw material that produces SiO gas is heated, to produce SiO gas, in the temperature range of 500～1100 DEG C, the SiO gas of described generation is supplied with to carbonaceous gas, making carbon content is 0.5～30% carbon containing Si oxide deposition.
By manufacturing like this carbon containing Si oxide, can effectively make carbon content is 0.5～30% carbon containing Si oxide deposition, can manufacture a kind of Si oxide in highly productive ground, described Si oxide can be made the non-aqueous electrolyte secondary cell negative electrode material that a kind of cell container is high and cycle characteristics is excellent.
Now, preferably: the raw material of aforementioned generation SiO gas is the mixture of silicon oxide powder or SiO 2 powder and silicon metal powder.
By using this raw material, can produce efficiently SiO gas, can further improve the productivity of non-aqueous electrolyte secondary cell negative electrode material Si oxide.
Now, preferably: in the time that the raw material of aforementioned generation SiO gas is heated, in existing under rare gas element or decompression, in the temperature range of 1100～1600 DEG C, heat.
By heating like this, reaction will be carried out efficiently, and produces sufficient SiO gas, can further improve the productivity of non-aqueous electrolyte secondary cell negative electrode material Si oxide.
Preferably: aforementioned carbonaceous gas is by C nh 2n+2the hydrocarbon gas that (n=1～3) represent.
If this hydrocarbon gas, due to favourable aspect cost, therefore, can be manufactured non-aqueous electrolyte secondary cell negative electrode material Si oxide at an easy rate.
In addition, provide a kind of lithium-ion secondary cell, it is characterized in that, it uses non-aqueous electrolyte secondary cell negative electrode material Si oxide of the present invention.
Like this, if use non-aqueous electrolyte secondary cell negative electrode material Si oxide of the present invention, can become the lithium-ion secondary cell of a kind of heavy body and cycle characteristics excellence.
In addition, provide a kind of electrochemical capacitor, it is characterized in that, it uses non-aqueous electrolyte secondary cell negative electrode material Si oxide of the present invention.
Like this, if use non-aqueous electrolyte secondary cell negative electrode material Si oxide of the present invention, can become the electrochemical capacitor of a kind of heavy body and cycle characteristics excellence.
[effect of invention]
As mentioned above, according to the present invention, a kind of non-aqueous electrolyte secondary cell negative electrode material Si oxide of high-quality can be provided, and described Si oxide, in the situation that using as negative material, can be made the rechargeable nonaqueous electrolytic battery that a kind of cell container is high and cycle characteristics is excellent.
Brief description of the drawings
Fig. 1 is the synoptic diagram that represents the horizontal tubular furnace using in embodiment, comparative example.
Embodiment
The inventor is conceived to the active substance of the cell container that improves carbon material, namely silicon oxide series negative material, and be that active substance is studied to the silicon that can maintain heavy body and there is the cycle characteristics identical with carbon material.
Result is clear and definite by namely forming conductive network on the negative material of Si oxide at insulating material, will significantly improve cycle characteristics, and the possibility that discovery can realize above-mentioned purpose is higher.And, the inventor makes great efforts to study to the method that forms conductive network on the negative material of Si oxide, found that in the time making SiO gas aggradation and manufacture Si oxide, by jointly depositing with carbonaceous gas, can obtain with comparalive ease the carbon containing Si oxide with electroconductibility, by be used for non-aqueous electrolyte secondary cell negative electrode material using this carbon containing Si oxide as active substance, can obtain the rechargeable nonaqueous electrolytic battery of heavy body and cycle characteristics excellence, thereby complete the present invention as described below.
Below, for the present invention, at length describe with the form of an example of embodiment, but the invention is not restricted to this embodiment.
Non-aqueous electrolyte secondary cell negative electrode material Si oxide of the present invention is carbon containing Si oxide, and described carbon containing Si oxide is that carbon content is 0.5～30% by supply with namely carbonaceous gas jointly deposit and obtain of carbon source in the time making SiO gas aggradation.
If this carbon containing Si oxide in the time using as non-aqueous electrolyte secondary cell negative electrode material, can become heavy body, and can obtain excellent cycle characteristics.
If the carbon content of carbon containing Si oxide of the present invention is less than 0.5%, in the time using as non-aqueous electrolyte secondary cell negative electrode material, compared with common Si oxide, do not confirm the raising of cycle characteristics.On the contrary, if carbon content is higher than 30%, although confirm the raising of cycle characteristics, cell container reduction.In addition, improve in order to ensure cycle characteristics, carbon content is preferably 1～25%, and more preferably 1.5～20%.
In addition, preferably: the not SiCization of carbon that carbon containing Si oxide of the present invention is contained.
Like this, if not SiCization of the carbon containing can be made a kind of rechargeable nonaqueous electrolytic battery, it positively prevents the deteriorated of cell container and cycle characteristics, and demonstrates excellent cell container and cycle characteristics.
In addition, the physical property in the present invention except the carbon content of carbon containing Si oxide is not particularly limited, but median size is preferably 0.1～30 μ m, is particularly preferably 0.2～20 μ m.
Median size is more than 0.1 μ m, and particularly particle more than 0.2 μ m is easily manufactured, and specific surface area is less, and the ratio of the silicon-dioxide of particle surface diminishes.Therefore,, in the time using as non-aqueous electrolyte secondary cell negative electrode material, it is higher that cell container becomes.In addition, if median size is 30 xbelow m, particularly, below 20 μ m, in the time coating electrode, be not easy to become impurity, can prevent the reduction of battery behavior.
This median size for example can use the weight average particle diameter in the particle size distribution of being implemented by laser diffractometry to represent.
In addition, the BET specific surface area of carbon containing Si oxide of the present invention is preferably 0.5～30m 2/ g, is particularly preferably 1～20m 2/ g.
If BET specific surface area is 0.5m 2more than/g, particularly 1m 2more than/g, the cementability while coating electrode is good, and it is good that battery behavior becomes.On the other hand, if at 30m 2below/g, particularly 20m 2below/g, the ratio of the silicon-dioxide of particle surface diminishes, and in the time using as non-aqueous electrolyte secondary cell negative electrode material, cell container uprises.
Then, the non-aqueous electrolyte secondary cell negative electrode material of manufacturing the invention described above is described by the method for Si oxide.
In manufacture method of the present invention, the raw material that produces SiO gas is heated, to produce SiO gas, in the temperature range of 500～1100 DEG C, the SiO gas of described generation is supplied with to carbonaceous gas, making carbon content is 0.5～30% carbon containing Si oxide deposition.
If this present invention, can effectively make carbon content is that 0.5～30% carbon containing Si oxide deposition obtains, and can manufacture that productivity is good, the non-aqueous electrolyte secondary cell negative electrode material Si oxide of high-quality.
In addition, carbon content is for example measured by oxygen combustion method, as concrete determinator, can list hole field and make the metal carbon analyzer EMIA-110 of institute (HORIBA, Ltd.).
At this, SiO gas (silicon oxide gas) is by the raw material that produces SiO gas is heated and obtained, and as the raw material that now produces SiO gas, preferably uses silicon oxide powder or SiO 2 powder and by the mixture of the powder of its reduction.
Like this, if the mixture of silicon oxide powder or SiO 2 powder and reduced powder can produce sufficient SiO gas.As concrete reduced powder, can list metallic silicon compounds, carbonaceous powder etc., particularly use in the situation of silicon metal powder, comparatively effective aspect (1) raising reactivity, (2) raising output, preferably use.
Now, suitably select the blending ratio of silicon metal powder and SiO 2 powder, consider the existence of the micro amount of oxygen in Surface Oxygen and the Reaktionsofen of silicon metal powder, mix mol ratio and be preferably 1 < silicon metal powder/SiO 2 powder < 1.1, be particularly preferably the scope of 1.01≤silicon metal powder/SiO 2 powder≤1.08.
In addition, preferably: in the time that above-mentioned raw materials is heated to produce SiO gas, by heating raw materials and remain on 1100～1600 DEG C, the temperature of 1200～1500 DEG C particularly, generate SiO gas.
If temperature of reaction is more than 1100 DEG C, particularly more than 1200 DEG C, reaction will be carried out efficiently, and the growing amount of SiO gas is abundant.In addition, if below 1600 DEG C, particularly below 1500 DEG C, raw material can melting, and reactivity can maintain higher state, and produces the SiO gas of q.s, and in addition, temperature can be not too high, thereby stove material is not limited.
In the time of this heating, furnace inner environment is preferably and exists under rare gas element or decompression, from the viewpoint of thermodynamics, because reactivity under the environment in decompression is higher, can carry out low-temp reaction, so more preferred.
Therefore, preferably, under the environment of decompression, with 1～200Pa heating raw, particularly preferably with 5～100Pa, raw material is heated.
In addition, the carbonaceous gas of supplying with when making this SiO gas aggradation, is not particularly limited, and form is supplied with as follows: by C nh 2n+2the hydrocarbon gas that (n=1～3) represent; The alkylol cpd such as methyl alcohol, ethanol; The aromatic hydrocarbons of 1 ring～3 rings such as benzene,toluene,xylene, vinylbenzene, ethylbenzene, ditan, naphthalene, phenol, cresols, oil of mirbane, chlorobenzene, indenes, coumarone, pyridine, anthracene, phenanthrene and the mixture of these compounds; Or the mixture of the rare gas elementes such as these reducing gas and Ar, He gas.
Wherein, particularly due to by C nh 2n+2the hydrocarbon gas that (n=1～3) represent is also more favourable aspect cost, therefore, can preferably use.
The deposition of carbon containing Si oxide is in the time making above-mentioned SiO gas aggradation, to supply with carbonaceous gas, for example, can on depositing base, jointly deposit, and the temperature range of deposition is set in to 500～1100 DEG C.
If depositing temperature is lower than 500 DEG C, the pyrolysis rate of carbonaceous gas reduces, and can make not contain completely the Si oxide deposition of carbon, in addition, forms needing for a long time containing silicon oxide carbide of carbon content of the present invention, and unrealistic.On the contrary, if higher than 1100 DEG C, in the reacting of SiO gas and carbonaceous gas, can generate SiC (silicon carbide), in the time using as negative material, the battery behaviors such as capacity, cycle characteristics significantly reduce.In addition, consider sedimentation effect etc., particularly preferably depositing temperature is 700～1000 DEG C.
The control of the temperature of sediment chamber can utilize heater heats, heat-proof quality (thickness of lagging material), force cooling etc. suitably to carry out.
In addition, the kind of the depositing base of carbon containing Si oxide deposition is also not particularly limited, from the viewpoint of processibility, preferably uses the refractory metals such as stainless steel (SUS) or molybdenum, tungsten.
The carbon content of the carbon containing Si oxide of manufacturing can be passed through flow, the time etc. of supplied with carbonaceous gas and easily control.
The carbon containing Si oxide depositing on depositing base as above, can be as required, utilizes appropriate means to pulverize, for example, form above-mentioned preferred median size, BET specific surface area.
Will manufacture as described above the non-aqueous electrolyte secondary cell negative electrode material of the present invention Si oxide that forms when negative material uses, in order further to increase electroconductibility, preferably: process or machine-alloying by chemical vapor deposition, to the non-aqueous electrolyte secondary cell negative electrode material being obtained by the present invention Si oxide carbon coated.
Now, also can be under normal pressure or under decompression, with 600～1200 DEG C, preferably the temperature of 800～1100 DEG C imports gas and/or the steam of hydrocarbon system compound, by implementing known thermochemistry vapor deposition treatment etc., form a kind of silicon composite particle precursor, its particle surface at carbon containing Si oxide forms carbon film, meanwhile, has silicon carbide layer at the interface formation of silico-carbo layer.
As hydrocarbon system compound, select to generate carbon compound with above-mentioned thermal treatment temp pyrolysis, for example, except methane, ethane, propane, butane, pentane and hexane etc., can also list: independent hydrocarbon or its mixtures such as ethene, propylene, butylene and acetylene; The alkylol cpd such as methyl alcohol, ethanol; The aromatic hydrocarbonss of 1 ring～3 rings such as benzene,toluene,xylene, vinylbenzene, ethylbenzene, ditan, naphthalene, phenol, cresols, oil of mirbane, chlorobenzene, indenes, coumarone, pyridine, anthracene and phenanthrene or these mixture.In addition, also can be separately or the form of mixture use the gas lightweight oil, creosote, carbolineum, the petroleum naphtha that are obtained by tar distillation technique to decompose tar.
In addition, the in the situation that of carbon coated, carbon covering amount is preferably: 1～50 quality % of the Si oxide of carbon coated, is particularly preferably 1～20 quality %.
As mentioned above, can process with Si oxide the non-aqueous electrolyte secondary cell negative electrode material being obtained by the present invention, manufacture lithium-ion secondary cell.
Now, the lithium-ion secondary cell of manufacturing is characterised in that and uses non-aqueous electrolyte secondary cell negative electrode material Si oxide of the present invention, material and the cell shapes etc. such as positive pole in addition, ionogen, barrier film can be used known material and shape, do not limit.
For example, as positive active material, can use LiCoO 2, LiNiO 2, LiMn 2o 4, V 2o 5, MnO 2, TiS 2and MoS 2deng oxide compound and the chalcogen compound etc. of transition metal.As ionogen, for example, use the non-aqueous solution that comprises the lithium salts such as lithium perchlorate; As non-aqueous solvent, by propylene carbonate, NSC 11801, glycol dimethyl ether, gamma-butyrolactone, 2-methyltetrahydrofuran etc. with monomer or combine two or more forms and use.In addition, also can use various non-water system ionogen or solid electrolyte in addition.
In addition,, in the case of using the secondary battery cathode material being obtained by the Si oxide of the invention described above to make negative pole, can in secondary battery cathode material, add the conductive agents such as graphite.Now, the kind of conductive agent is also not particularly limited, and decomposes or the material of rotten electroconductibility as long as not causing in the battery forming.Specifically, can use the graphite such as the metal-powders such as Al, Ti, Fe, Ni, Cu, Zn, Ag, Sn and Si, steel fiber or natural graphite, synthetic graphite, various coke powder, mesocarbon, gas-phase growth of carbon fibre, pitch-based carbon fiber, PAN based carbon fiber, various resin sintered compacies.
In addition, in the situation that obtaining electrochemical capacitor, electrochemical capacitor is characterised in that, uses the Si oxide (active substance) of the invention described above on electrode, and the materials such as other ionogen, barrier film and electrical condenser shape etc. are also unrestricted.For example, as ionogen, use the non-aqueous solution of lithium salts such as comprising lithium hexafluoro phosphate, lithium perchlorate, boron lithium fluoride, arsenic hexafluoride acid lithium; As non-aqueous solvent, by propylene carbonate, NSC 11801, methylcarbonate, diethyl carbonate, glycol dimethyl ether, gamma-butyrolactone and 2-methyltetrahydrofuran etc. with monomer or combine two or more forms and use.In addition, also can use various non-water system ionogen or solid electrolyte in addition.
If lithium-ion secondary cell or the electrochemical capacitor of Si oxide for use as above non-aqueous electrolyte secondary cell negative electrode material of the present invention, can form secondary cell or the electrochemical capacitor of the battery behavior such as cell container and cycle characteristics excellence.
[embodiment]
Below, embodiment and comparative example are shown, are described more specifically the present invention, but the invention is not restricted to this.
(embodiment 1)
Manufacture carbon containing Si oxide with the horizontal tubular furnace 10 of Fig. 1.Reaction tubes 1 is the oxidation aluminum reaction tubes of internal diameter 80mm, by the silicon metal powder of median size 5 μ m and aerosil (fumed silica) powder (BET specific surface area: 200m 2/ g) wait molar mixture as raw material 2, in reaction tubes 1, pack the raw material 2 of 50g into.
Then, carry out exhaust with vacuum pump 7, make to be decompressed to below 20Pa in stove, and utilize well heater 6, be warming up to 1400 DEG C with the heat-up rate of 300 DEG C/h.In addition, heat with deposition portion well heater 8 simultaneously, the deposition portion that disposes depositing base 3 is remained on to 700 DEG C.Reach after 1400 DEG C at raw material, utilize under meter 4, flow into CH with the flow of 1NL/ minute from gas introduction tube 5 4gas (press in stove and rise to 100Pa).Carrying out this running after 3 hours, stop CH 4the inflow of gas and heater heats, be cooled to room temperature.
After cooling, the settling of deposition on depositing base 3 is reclaimed, settling is black block, and yield is 41g.
Then, with the oxidation aluminum ball mill of 2L, this settling of 30g is carried out to dry type pulverizing, manufacture non-aqueous electrolyte secondary cell negative electrode material Si oxide.
The Si oxide obtaining is median size 7.5 μ m, BET specific surface area 4.3m 2the powder of/g, carbon content 5.3%.
[cell evaluation]
Then, in accordance with the following methods, the battery that uses the processing powder of the Si oxide obtaining to be used as negative electrode active material is evaluated.
First, in the processing powder obtaining, add 45 weight (wt) % synthetic graphite (median size 10 μ m), the polyimide of 10 weight (wt) %, and then interpolation N-Methyl pyrrolidone, to form slurry, this slurry is coated on the Copper Foil of thickness 12 μ m, after being dried 1 hour with 80 DEG C, utilize roll squeezer press molding electrode, this electrode after 1 hour, is struck out to 2cm 350 DEG C of vacuum-dryings 2, form negative pole.
At this, for the charge-discharge characteristic of the negative pole obtaining is evaluated, make an evaluation lithium-ion secondary cell, described lithium-ion secondary cell be to use lithium paper tinsel to electrode, use and lithium hexafluoro phosphate be dissolved in to the 1/1(volume ratio of NSC 11801 and diethyl carbonate with the concentration of 1 mole/L) form non-aqueous electrolytic solution in mixed solution and be used as nonaqueous electrolyte, barrier film is the polyethylene microporous film of used thickness 30 μ m.
The lithium-ion secondary cell being made was at room temperature placed after the evening, used charging/discharging of secondary cell testing apparatus ((thigh) NAGANO system), with 0.5mA/cm 2continuous current charge, until the voltage of test battery reaches 0V, reach after 0V, reduce electric current to cell voltage is remained on to 0V, and charge.And, at current value lower than 40 μ A/cm 2moment complete charge.Electric discharge is with 0.5mA/cm 2continuous current carry out, cell voltage higher than the moment of 2.0V finish electric discharge, obtain loading capacity.
Repeat the above test that discharges and recharges, evaluate with the test that discharges and recharges after lithium-ion secondary cell 50 circulations.The following item of results verification: the circulation conservation rate 98% after loading capacity 1070mAh/g, 200 circulations of primary charging capacity 1440mAh/g, first loading capacity 1090mAh/g, first efficiency for charge-discharge 75.7%, the 200th circulation, lithium-ion secondary cell is heavy body and first efficiency for charge-discharge and cycle characteristics excellence.
(embodiment 2)
Replace CH with acetylene gas 4gas, is made as 550 DEG C by deposition portion temperature, in addition, according to the method identical with embodiment 1, manufactures non-aqueous electrolyte secondary cell negative electrode material Si oxide.
The Si oxide obtaining is median size 7.6 μ m, BET specific surface area 14.3m 2the powder of/g, carbon content 2.2%.
Then, make negative pole according to the method identical with embodiment 1, battery is evaluated.The following item of results verification: the circulation conservation rate 98% after loading capacity 1080mAh/g, 200 circulations of primary charging capacity 1460mAh/g, first loading capacity 1100mAh/g, first efficiency for charge-discharge 75.3%, the 200th circulation, lithium-ion secondary cell is heavy body and first efficiency for charge-discharge and cycle characteristics excellence.
(embodiment 3)
The acetylene gas scale of construction is made as to 1.5NL/min, deposition portion temperature is made as to 1000 DEG C, in addition, manufacture non-aqueous electrolyte secondary cell negative electrode material Si oxide according to the method identical with embodiment 2.
The Si oxide obtaining is median size 7.5 μ m, BET specific surface area 2.8m 2the powder of/g, carbon content 22.5%.
Then, make negative pole according to the method identical with embodiment 1, battery is evaluated.The following item of results verification: the circulation conservation rate 98% after loading capacity 1000mAh/g, 200 circulations of primary charging capacity 1320mAh/g, first loading capacity 1020mAh/g, first efficiency for charge-discharge 77.3%, the 200th circulation, lithium-ion secondary cell is compared with embodiment 1,2, although volume lowering, first efficiency for charge-discharge and cycle characteristics excellence.
(comparative example 1)
Do not supplying with under the prerequisite of carbonaceous gas, making Si oxide deposition, in addition, manufacturing non-aqueous electrolyte secondary cell negative electrode material Si oxide according to the method identical with embodiment 1.
The Si oxide obtaining is median size 7.6 μ m, BET specific surface area 5.6m 2/ g, carbon-free powder.
Then, make negative pole according to the method identical with embodiment 1, battery is evaluated.The following item of results verification: the circulation conservation rate 90% after loading capacity 990mAh/g, 200 circulations of primary charging capacity 1460mAh/g, first loading capacity 1100mAh/g, first efficiency for charge-discharge 75.3%, the 200th circulation, compared with embodiment 1-3, the cycle characteristics of lithium-ion secondary cell is poor.
(comparative example 2)
The acetylene gas scale of construction is made as to 1NL/min, deposition portion temperature is made as to 450 DEG C, in addition, manufacture non-aqueous electrolyte secondary cell negative electrode material Si oxide according to the method identical with embodiment 2.
The Si oxide obtaining is median size 7.5 μ m, BET specific surface area 34.2m 2the powder of/g, carbon content 0.2%.
Then, make negative pole according to the method identical with embodiment 1, battery is evaluated.The following item of results verification: the circulation conservation rate 89% after loading capacity 940mAh/g, 200 circulations of primary charging capacity 1410mAh/g, first loading capacity 1060mAh/g, first efficiency for charge-discharge 75.1%, the 200th circulation, compared with embodiment 1-3, the cycle characteristics significance difference of lithium-ion secondary cell.
(comparative example 3)
The acetylene gas scale of construction is made as to 2NL/min, and deposition portion temperature is made as 1000 DEG C, in addition, manufactures non-aqueous electrolyte secondary cell negative electrode material Si oxide according to the method identical with embodiment 2.
The Si oxide obtaining is median size 7.5 μ m, BET specific surface area 3.2m 2the powder of/g, carbon content 33.4%.
Then, make negative pole according to the method identical with embodiment 1, battery is evaluated.The following item of results verification: the circulation conservation rate 98% after loading capacity 960mAh/g, 200 circulations of primary charging capacity 1260mAh/g, first loading capacity 980mAh/g, first efficiency for charge-discharge 77.8%, the 200th circulation, compared with embodiment 1-3, the cell container significance difference of lithium-ion secondary cell.
(comparative example 4)
Deposition portion temperature is made as to 1150 DEG C, in addition, manufactures non-aqueous electrolyte secondary cell negative electrode material Si oxide according to the method identical with embodiment 1.
The median size of the Si oxide obtaining is 7.5 μ m, and BET specific surface area is 1.1m 2/ g, by X-ray diffraction analysis, confirms Formed SiClx (SiC).
Then, make negative pole according to the method identical with embodiment 1, battery is evaluated.The following item of results verification: the circulation conservation rate 76% after loading capacity 720mAh/g, 200 circulations of primary charging capacity 1300mAh/g, first loading capacity 950mAh/g, first efficiency for charge-discharge 73.2%, the 200th circulation, compared with embodiment 1-3, the cell container of lithium-ion secondary cell, first efficiency for charge-discharge, cycle characteristics significance difference.
In addition, the present invention is not limited to above-mentioned embodiment.Above-mentioned embodiment is for illustrating, and all inventions that have the formation identical in fact with technological thought described in claims of the present invention and bring into play same function effect are all included in technical scope of the present invention.

Claims (9)

1. a non-aqueous electrolyte secondary cell negative electrode material Si oxide, is characterized in that, it is the carbon containing Si oxide by the common deposition of SiO gas and carbonaceous gas is obtained, and the carbon content of described carbon containing Si oxide is 0.5～30%.
2. non-aqueous electrolyte secondary cell negative electrode material Si oxide as claimed in claim 1, wherein, the not SiCization of carbon that aforementioned carbon containing Si oxide is contained.
3. non-aqueous electrolyte secondary cell negative electrode material Si oxide as claimed in claim 1 or 2, wherein, the median size of aforementioned carbon containing Si oxide is 0.1～30 μ m, BET specific surface area is 0.5～30m 2/ g.
4. the manufacture method of a non-aqueous electrolyte secondary cell negative electrode material use Si oxide, it is the method for manufacturing non-aqueous electrolyte secondary cell negative electrode material Si oxide, it is characterized in that, the raw material that produces SiO gas is heated, to produce SiO gas, in the temperature range of 500～1100 DEG C, the SiO gas of described generation is supplied with to carbonaceous gas, making carbon content is 0.5～30% carbon containing Si oxide deposition.
5. the manufacture method of Si oxide for non-aqueous electrolyte secondary cell negative electrode material as claimed in claim 4, wherein, the raw material of aforementioned generation SiO gas is the mixture of silicon oxide powder or SiO 2 powder and silicon metal powder.
6. the manufacture method of Si oxide for the non-aqueous electrolyte secondary cell negative electrode material as described in claim 4 or 5, wherein, in the time that the raw material of aforementioned generation SiO gas is heated, existing under rare gas element or decompression, in the temperature range of 1100～1600 DEG C, heat.
7. the manufacture method of Si oxide for the non-aqueous electrolyte secondary cell negative electrode material as described in any one in claim 4～6, wherein, aforementioned carbonaceous gas is by C nh 2n+2the hydrocarbon gas representing, n=1～3.
8. a lithium-ion secondary cell, is characterized in that, its right to use requires the non-aqueous electrolyte secondary cell negative electrode material Si oxide described in any one in 1～3.
9. an electrochemical capacitor, is characterized in that, its right to use requires the non-aqueous electrolyte secondary cell negative electrode material Si oxide described in any one in 1～3.
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